N, n&#39;-dinitro dicarbamates



United States Patent C N,N'-D1NITRO DICARBAMATES Milton B. Frankel, Pasadena, Calif., assignor to Aerojet- General Corporation, Azusa, Califl, a corporation of Ohio No Drawing. Filed Nov. 5, 1954, Ser. No. 466,969

20 Claims. (Cl. 260-482) This invention relates to new compositions of matter and a method for their preparation. In particular, it relates to N,N'-dinitro dicarbamates having the general formula:

N02 N0, N0: o .l t l. l i

L J: wherein R and R' are nitroalkyl radicals, A and A are radicals selected from the group consisting of alkyleneand nitroalkylene radicals, and x is a. small whole number from 0 to 5 inclusive. r

The compounds of this invention are prepared by reacting nitrocarbamates with nitric acid, in accordance with the general reaction scheme set forth below:

wherein R, R', A, A, and x are as defined above.

The reaction is preferably conducted at a temperature recrystallizations from chloroform gave white needles,

EXAMPLE II Preparation of N,N'-dinitr0-3,3-dinitro-1,S-pentanebis(2,2,2-trinitr oethyl dicarbamate) A nitration mixture of 50 ml. of 100% nitric acid and 50 ml. of acetic anhydride was cooled in an ice bath and 5.0 gm. of 3,3-dinitro-1,S-pentane-bis(trinitroethyl dicarbamate) was added. The reaction mixture was stirred in the range of from about 0 to about 15 C. The reaction can be performed at higher temperatures, however, it is preferred to run the reaction at reduced temperatures to permit better control of the reaction rate. Increased smoothness and control of the nitration is achieved when the reaction is conducted in the presence of an alkanoic anhydride.

The dicarbamates used as starting materials are prepared by the addition of nitro alcohols to diisocyanates, as disclosed in my copending application No 464,610, filed October 25, 1954. To more clearly illustrate my invention, the following examples are presented.

scope of the invention in any way.

EXAMPLE I Preparation of N,N-dinitr0-methyIene-bis(2,2,2-tri-' nitroethyl dicarbamate) It should be understood, however, that these examples are presented merely as a means of illustration and are not intended to limit the "H, 1.86; percent N, 25.77. Found: "percent H, 2.23; percent N, 25.87. p

Calculated heat of combustion: 1792 cal/gm. Found: l 1826 cal/gm.

for 20 minutes. and poured 'onto' ice. The white solid wascollected, washed with water, and dried to give 4.9 gm. of product, M.P. 148-150" C. Two recrystallizations from methylene chloride raised.the melting point to 151-152" C., impact stability=2530 cm./2 kg. The elementalanalysis of the product is as follows:

Calculated for C H N O percent C, 18.97; percent H, 1.74; percent N, 24.14. Found: percent C, 19.19; percent H, 'l.77; percent" N, 23.87. A Calculated heat of combustion: 1784 caljgm, Found: 1776 caL/gm.

Calculated lead block value: 165 TNT=100. Calculated ballistic mortar value: 140 TNT=100.

EXAMPLE III Preparation 0]? N,N"-dinitr0-3-nitraza-L5-pentane bis(2,2,2-trinitr0ethyl dicarbamate) Ten ml. of nitric acid was cooled to 0 C. and 10 ml. of acetic anhydride was added dropwise. 'To the solution was added 0.5 gm. of B-nitraza-1,5-pentane-bis- (2,2,2-trinitroethyl dicarbamate). While maintaining the temperature at about 5-10 C., the solution was stirred for 20 minutes. The solution was then poured ove'r ice. The resulting white solid was recrystallized from ethylenedichloride in 86.3% yield, M.P. -122 C. The elemental analysis of the product is as follows: 7

Calculated for C H N O percent C, 18.41 percent Calculated lead block value: 162 TN'I=100. Calculated ballistic mortar value: TNT=100.

, EXAMPLE IV Preparation of N,N'-d initr0-3,3,5,7,7-pentanitro-5-aza-l nonane-bis(2,2,2-trinitroethyl dicarbamate) follows:

vacuo. The yield of methylene N,N"-dinitro-bis(trinitroethyl dicarbamate) was 1.2 gm., M.P. 92-93 C. Three cent H, 1.82; percent N, 25.23.: Found: percentC, 19.1'2; percent H, 1.84; percent N, 25.19.

- -ratente'd p 41 95 i 7 percent C, 18598;

dicarbamate) will react with nitric acid to produce N,N-

of this invention in a device such as that disclosed in 76 United States Patent No. 2,470,162, is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sutficiently a insensitive to withstand the-shock entailed in the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of an impactor time fuse-mechanism firing a detonating explosive such as lead azide or mercury fulminate.

I claim:

1. As compositions of matter, N,N'-dinitro dicarbamates having the general formula:

Calculated heat of combustion: 1857 cal./gm. Found: 1946 cal./gm.

Calculated lead block value: 164 TNT=100.

Calculated ballistic mortar value: 142 TNT=100.

EXAMPLE V Preparation of N,Ndir iitro-3,6-nitraza-1,8-octane-bis- (2,2,2-trinitrethyl dicarbamate) Ten ml. of 100% nitric acid was-cooled to 0 C. and 10 ml. of acetic anhydride was added dropwise. To the solution was added 0.5 gm. of 3,6-nitraza-1,8-octanebis(2,2,2-trinitroethyl dicarbamate). While maintaining the temperature at about 5-10 C., the solution was stirred for 20 minutes. The solution was then poured over ice.. The resulting white solid was recrystallized 0 0 from 70% nitric acid in 87.8% yield, M.P. 127-128 C. ll l i l I l g The elemental analysis of the product is as follows: L

Cal ulated f0 C H N O ercent C, 19.47- ercent g j f g percemc 15 wherein R and R are lower mtroalkyl radicals, A and percen; H percent N 25'73 A are radicals selected from the group consisting of calculaieid a block vame: 142 TNT=10O lower alkylene and lower nitroalkylene radicals, and x Calculated ballistic mortar value: 141 TNT=100. a small whole Pf of 0 to 5 f 2. As a composition of matter, N,N -din1tromethylene- EXAMPLE VI bis(2,2,2-trinitroethyl dicarbamate) having the structural Preparation of N,N-dinitro-Z-nitraza-d,4-butane-bisformula? (2,2,2-trinitroethyl dicarbamate) N02 0 N01 N02 0 No, In a one-liter three-necked flask, fitted with a mechanil l cal stirrer, thermometer, and dropping funnel, was placed 1 L 200 ml. of technical 100% nitric acid. The flask was cooled in an ice-salt bath, and 200 ml. of acetic anhy- 3. As a composition of matter, N,N'-dinitro-3,3-didride was added dropwise, keeping the temperature below nitro 1,5 pentane-bis(2,2,2 trinitroethyl dicarbamate) 10 C. 25.0 gm. quantity of 2-nitraza- 1,4-butane-bishaving the structural formula: (2,2,2-trinitroethyl dicarbamate) was added portionwise. O N O N a The solution was stirred at 5-10 C. for 15 minutes and I\lmi l g I Ii T poured on ice. The white gummy solid Was collected NOI'C-CHTO-O-N'CHICHT and dried in vacuo over potassium hydroxide; the weight N0, N0; N0, was 18.3 gm. (62.8%). Several recrystallizations from ethylene dichloride gave white needles, M.P. 113-114 C. AS gF a fi g SB h The elemental analysis of the product is as follows: 40 i y lcarbamate) having Calculated-for C H N O percent C, 16.94; pert e Structura cent H, 1.58; percent N, 26.34. Found: percent C, 16.98; 1702 1T0, 1110, a lot (d N0, P PF NO -CCHg-OC-N-CHiCHr-N-CH2CH2-N'C-OCHr-NO By proceeding in accordance with the examples set forth above, I have also found that dicarbamates such as methylene-bis(3,3-dinitropropyl dicarbamate), 3,5,5- 5. As a composition of matter, N,N-dinitro-3,3,5,7,7- trinitro-3-aza-1,8-octane-bis-(2,2,2-trinitroethyl dicarbampentanitro-S-aza-l,9-nonane-bis(2,2,2-trinitroethyl dicarate), and 3,3-dinitro-1,5-pentane-bis(3,3,3-trinitropropyl bamate) having the structural formula:

No, 1? N0: I IO, N0, N0, N0; (fi N10, NO J-OH -O-G-bi-CHgClh-(i-CH -cH,C-CH,oH2-I i-c-0-0H-(3-No, N0, N0: N0, N0,

6. As a composition of matter, N,N-dinitro-3,6-nitraza-l,8-octane-bis(2,2,2-trinitroethyl dicarbamate) havdinitromethylene-bis(2,2-dinitropropyl dicarbamate), 5

ing the structural formula:

N-dinitro-3,5,5-trinitro-3-aza-1,8-octane-bis(2,2,2 trini- 7. As a composition of matter, N,N-dinitro-2-nitraza- 1,4 butane bis(2,2,2 trinitroethyl dicarbamate) having the structural formula:

troethyl dicarbamate), and N,N-dinitro-3,3-dinitro-1,5- pentane-bis-(3,3,3-trinitropropyl dicarbamate), respectively.

It is apparent from the above discussion that any mem- 0 N02 N02 NO, 0 N02 ber of the N,N'-dinitro dicarbamate series may be prel l I l pared by merely selecting the appropriate dicarbamate Nora? and reacting it with nitric acid, in accordancewith the teachings of this invention.

The nitro compounds of this invention are useful as 8. As a composition of matter, N,N'-dinitromethylenebis(2,2-dinitropropyl dicarbamate) having the structural high explosives and can be used in any conventional 7 formula:

explosive missile, projectile, rocket, or the like, as the N0 0 NO: NO, 0 N02 main explosive charge. An example of such a missile l! I ll 1 is disclosed in United States Patent No. 2,470,162, issued CH?- May 17, 1949. One way of using the high explosives ;9..Asa composition of matter, N,N'-dinitro-3,5,5-tri- 6 nitro-3-aza-1,8-octane-bis(2,2,2-trinitroethyl dicarbamate) comprises reacting nitric acid with 3-nitraZa-LS-pentanehaving the structural formula: bis(2,2,2-trinitroethyl dicarbamate).

NO: 0 N01 N01 NO| I110: (If I |]'Og NO:$CHr-OCNCHzCHz-N-GIL-(i7-CHzCHr-CHrNCO-CHz-(E-NO;

N0, N01 N02 10. As a composition of matter, N,N'-dinitro-3,3-di- 15. The method of preparing N,N'-dinitro-3,3,5,7,7-, nitro 1,5 pentane-bis(3,3,3-trinitropropyl dicarbamate) pentanitro-S-aza-l,9-nonane-bis(2,2,2,-trinitroethyl dicarhaving the structural formula: bamate) which comprises reacting nitric acid with N0; g NO, NO: NO: (I? N02 N03- -CHgCHa-QC-NOH:CHr+--CH:CHr-N-C-O-CHzCHr-+NO,

l lo: N 0: N 2 11. The method of preparing N,N-dinitro dicar- ,7,-pentanitro-5-aza-1,9-nonane-bis(2,2,2 trinitrobamates having the general formula: ethyl dicarbamate).

16. The method of preparing N,N-dinitro-3,6-nitraza- E lfml" lil I 1 f 1,8-octane-bis(2,2,2-trinitroethyl dicarbamate) which R-OO-N--AN-ANCOR comprises reacting nitric acid with 3,6-nitraza-1,8-octane- L x bis(2,2,2-trinitroethyl dicarbamate).

17. The method of preparing N,N'-dinitro-2-nitrazawhlch compmes reactmg mmc acid Wltha carbamate 1,4-butane-bis(2,2,2-trinitroethyl dicarbamate) which having the general formula: comprises reacting nitric acid with 2-nitraza-l,4-butanebis(2 2 Z-trinitroethyl dicarbamate).

0 H N0 H o i I a 0 R, 18. The method of preparing N,N-dinitromethylene- "E A bis(2,2-dinitropropyl dicarbamate) which comprises reacting nitric acid with methylene-bis(2,2-dinitropropyl diwherein R and R are lower nitroalkyl radicals, A and cialrbllrlatel i A are radicals selected from the group consisting of The method of p p N,N lower alkylene and lower nitroalkylene radicals, and x is Intro 3 OC tane-b1S( 2,2,2 trinitroethyl dlcara small whole number from 0 to 5 inc1usive bamate) WhlCh comprises reacting nitric and with 3,5,5-

12. The method of preparing N,N'-dinitromethylenetl'initl'o 3 aZa 1,s-octafle-bis(2,2,2-tIi11itI0ethY1 dical bis(2,2,2-trinitroethyl dicarbamate) which comprises barman?)- 0 reacting nitric acid with methylene-bis(2,2,2-trinitroethyl The of P p dicarbamate). 1,5-pentane-b1s(El,3,3-tr n1tropropyl drcarbamatel which 13. The method of preparing N,N'-dinitro-3,3-dinitro- P reactme 111t1'1c acld 'Wlth -L 1,5-pentane-bis(2,2,2-trinitroethyl dicarbamate) which i p py dlcafbamate) comprises reacting nitric acid with 3,3-dinitro-1,5- pentane-bis(2,2,2-trinitroethyl dicarbamate). References (Med 111 the file of this Patent 14. The method of preparing N,N'-dinitro-3-nitraza- 40 FOREIGN PATENTS 1,5-pentane-bis(2,2,2-trinitroethy1 dicarbamate) which 133 Sweden Dec. 23, 1952 

1. AS COMPOSITIONS OF MATTER N,N''DINITRO DICARBAMATES HAVING THE GENERAL FORMULA: 